The present invention relates to a hydrocarbon soluble or dispersible mixture of phosphorous- and/or sulfur-containing reaction products, their method of preparation, and their utility as antiwear and anti-oxidation additives for oleaginous compositions such as fuel oils, lubricating oils, including power transmission fluids and crankcase oils, and to the oleaginous compositions in which they are contained.
The lubrication of modern mechanical equipment requires that the lubricating oil possess excellent resistance to oxidation as well as the ability to protect metal surfaces in sliding or rolling contact from wear. These properties are vital to the success of any lubricating oil. Additives which improve the resistance of base lubricating oils to oxidation and extend the life of the equipment are of great importance.
Oxidation in lubricating oils manifests itself as an increase in acidity of the oil, increase in oil viscosity, and formation of insoluble products which appear as a sludge. Acidity in the oil is detrimental as it eventually leads to attack of the metal parts in the form of rusting or corrosion. Parts made of the yellow metals, copper, brass and bronze are especially susceptible to this type of attack. Increasing oil viscosity adversely effects the efficiency of the equipment and can lead to the inability to circulate the lubricant through the mechanism. Formation of sludge causes deposits in oil sumps and reservoirs. These deposits, if formed in small lubricant passageways or channels, can block lubricant flow. Excessive viscosity increase or sludge formation can cause failure due to lubricant starvation.
Wear results from the contact of metal surfaces in motion relative to each other. Under low loads and at high relative speeds hydrodynamic lubrication predominates. That is, the two metal parts are separated by a film of oil. This type of lubrication predominates in journal bearings. At higher loads or lower speeds the oil film fails and boundary lubrication becomes the main mechanism of lubrication. In boundary lubrication the two metal surfaces are separated only by a film of chemical additives. Gears operate in boundary lubrication mode. It is highly desirable that lubricating oils contain additives to provide for boundary lubrication conditions.
Control of friction is also possible through modifying the lubricating oil with additives. It is often desirable to modify the frictional performance of a lubricating oil but not necessarily to minimize it. For example, a specialized property sought to be imparted to certain lubricating oil compositions adapted for use as automatic transmission fluids and tractor hydraulic fluids is the ability to control friction to very exacting requirements. These requirements are set forth by the manufacturers of the equipment. This property distinguishes automatic transmission fluids (ATF's) and tractor hydraulic fluids (THF's) from other lubricants; and in fact, there is further differentiation between types of ATF's and THF's.
Such characteristic quality has received the most attention by both the transmission manufacturers and fluid producers for many years. The attention stems from the fact that the friction requirements of these fluids are unique and depend on the transmission and clutch or brake design, as well as on the type of friction materials used.
As is also well known, oxidation, wear and friction can be controlled through the addition of suitable additives with varying degrees of success.
While there are many known additives which may be classified as anti-wear, or friction modifying agents, it is also well known that many of these additives act in a different physical or chemical manner and often compete with one another, e.g. they may compete for the surface of the moving metal parts which are subjected to lubrication. Accordingly, extreme care must be exercised in selection of these additives to insure compatibility and effectiveness.
Both anti-wear and friction modifying agents function by forming a coating on the surface of the moving parts. The coating may be physically adsorbed or it may actually be bonded chemically to the surface. Consequently, if the association between the anti-wear agent and the metal part is stronger than the association between the friction modifying agent and the metal part, the anti-wear agent will displace the friction modifying agent at the metal surface, i.e. at the metal/fluid interface, and friction control will be lost.
Various tests have been designed by automatic transmission manufacturers for measuring ATF friction and anti-wear properties. These tests are used to evaluate the performance of additives and fluids in view of the requirements of particular transmission designs and their ability to impart transmission durability and smooth shifting under a variety of road conditions.
Frictional performance is typically evaluated on an SAE No. 2 friction apparatus. In this test, a test head containing a test clutch pack and the fluid is fitted to an electric motor with an inertia disc. The motor and flywheel of the friction machine (filled with fluid to be tested) are accelerated to constant speed, the motor is shut off and the flywheel speed is decreased to zero by application of the clutch. The clutch plates are then released, the system is again accelerated to constant speed, and the clutch pack which is immersed in the test fluid is engaged again. This process is repeated many times with each clutch engagement being called a cycle.
During the clutch application, friction torque is recorded as a function of time. The friction data obtained are either the torque traces themselves or friction coefficients calculated from the torque traces. The shape of the torque trace desired is set by the auto manufacturers. One way of characterizing this friction performance is to determine the torque: (a) when the flywheel speed is midway between the maximum constant speed selected and zero speed (such torque measurement is referred to herein as T.sub.D) and (b) when as the flywheel speed approaches zero rpm (such torque measurement is referred to herein as T.sub.0). Such torques can then be used to determine the torque ratio which is expressed as T.sub.0 /T.sub.D, or alternatively, to determine the torque differential T.sub.O -T.sub.D. The optimum target values for torque ratio and torque differential are set by the auto manufacturers. As the T.sub.0 /T.sub.D increasingly exceeds 1, a transmission will typically exhibit shorter harsher shifts as it changes gears. On the other hand as T.sub.0 /T.sub.D decreases below 1, there is an increasingly greater danger of clutch slippage when the transmission changes gears. Similar relationships exist with respect to a T.sub.0 -T.sub.D target value of 0.
While many automatic transmission fluids can achieve target values of T.sub.0 /T.sub.D after a minimum number of cycles, it becomes increasingly more difficult to sustain such target values as the number of cycles are increased. The ability of an ATF to sustain such desired friction properties is referred to herein as friction stability or durability. A high level of friction stability is difficult to achieve with ATFs containing certain anti-wear agents. It is believed that as the ATF ages under the influence of the heat of friction, the anti-wear agent can break down and the decomposition products displace conventional friction modifiers at the metal/fluid interface. As a result, the fluid may exhibit varying friction properties.
Attempts to improve friction stability by simply adding more friction modifier have not met with success because this tends to reduce the breakaway static torque (T.sub.S) of the fluid. This parameter when expressed as the breakaway static torque (T.sub.S) reflects the relative tendency of engaged parts, such as clutch packs, bands and drums, to slip under load. If this value is too low, the slippage can impair the driveability and safety of the vehicle.
Transmission designs have undergone radical changes, thereby necessitating the formulation of ATF additives capable of meeting new and more stringent requirements needed to match such design changes.
No base oil alone can even approach the many special properties required for ATF service. Therefore, it is necessary to employ several chemical additives, each of which is designed to impart or improve a specific property of the fluid. Consequently, it becomes particularly advantageous when one additive can perform more than one function, thereby reducing the number of additives needed to be present in the formulation.
Accordingly, there has been a continuing search for new additives possessed of one or more properties which render them suitable for use in ATF compositions, as well as other oleaginous compositions. There also has been a search for new combinations of additives which not only provide ATF compositions, as well as other oleaginous compositions, with the various specific properties that are required, but which are compatible with each other in the sense that they do not exhibit any substantial tendency to compete with each other, nor to otherwise reduce the effectiveness of the various additives in the compositions. The present invention was developed in response to this search.
U.S. Pat. No. 2,230,966 relates to stabilization of petroleum oils against oxidation by using thiosubstituted alkyl thio ethers of the general structure: EQU R'(SCR.sub.2 (CR.sub.2).sub.n).sub.x S((CR.sub.2).sub.m CR.sub.2 S).sub.y R'
wherein R represents hydrogen or an alkyl radical; wherein R' represents hydrogen or an alkyl, or aryl or an alkaryl radical (both R' need not be the same), wherein m, n, x and y are whole numbers. These materials are prepared by reaction of alkyl halides and alkyl di-halides with sodium sulfide. No oxygen containing analogues are included.
U.S. Pat. No. 2,346,154 relates to hydrocarbon oil compositions which contain a metal phenate stabilizer, a polyvalent metal salt of an acid of phosphorous containing an organic substituent and a thioether sensitizer which enhances the responsiveness of the hydrocarbon oil to stabilization by the phenate and salt. The thioether sensitizer is claimed as having the structural formula: EQU R--S--R.sub.1
or the structural formula: EQU R--S--CC--S--R.sub.1
wherein R and R.sub.1 are alkyl radicals, wherein at least one of R and R.sub.1 contains more than about ten carbon atoms, and wherein the sum of the sum of the number of carbon atoms in R and R.sub.1 is at least about twelve.
U.S. Pat. No. 2,522,512 relates to a process for preparing non-mineral oil base sulfur containing lubricating compositions, wherein a sulfur compound is mixed with a dialkenylether and heated in the presence of a minor amount of a catalyst to form a mixture of polymeric linear adducts of the reactants, and wherein the fraction which volatilizes below 160.degree. C. at 1 cm. mercury pressure is recovered from the polymeric adducts as product. The sulfur compound has the general formula: EQU R--S--R
wherein both R's are selected from the group consisting of hydrogen atoms and alkyl radicals, and at least one R is a hydrogen atom. The catalyst is selected from the group consisting of dialkylperoxides and alkyl hydroperoxides. The polymeric product contains compounds having units of the general configuration EQU --S--R--X--R--
wherein X is either S or O, depending upon whether an ether or thioether reactant was used, and each R is an organic radical, preferably a saturated hydrocarbon radical.
U.S. Pat. No. 2,562,144 discloses lubricating compositions containing one or more reaction products. One of the reactants is a polyether of the general formula EQU R.sub.1 [O--R--S--R].sub.n --O--R.sub.2
wherein R.sub.1 and R.sub.2 are mercaptoalkyl or alkenyl groups and R is a saturated hydrocarbon.
U.S. Pat. No. 2,566,157 discloses a lubricant having as the major ingredient thereof mixed partially isomeric triple ethers of the general formula: EQU A--S--B--O--B'--S--A'
wherein A, A', B and B' are saturated C.sub.2 -C.sub.18 aliphatic groups. The lubricant also contains a resin such as a polystyrene or acrylic resin, and an aralkyl ester ingredient which is intersoluble with the triple ether ingredient and a solvent of the resin.
U.S. Pat. No. 2,582,605 relates to a process for producing long chain sulfur and oxygen containing polyethers by reacting beta-hydroxyethyl sulfides with alcohols. The process consists of reacting any compound with the functional grouping-SCH.sub.2 CH.sub.2 OH with a hydroxy or polyhydroxy compound in the presence of a strong acid catalyst, preferably sulfuric acid or catalysts which may be considered as being derived from sulfuric acid, e.g. the aryl sulfonic acids or alkyl sulfonic acids (see Col. 8, lines 2-35). The reactions disclosed in this patent are carried out at elevated temperatures being about 130.degree. and 200.degree. C., and preferably between about 140.degree. C. and 160.degree. C.
U.S. Pat. No. 2,721,177 relates to poly-oxyalkylene glycol lubricating oil compositions having improved stability towards oxidative deterioration. The compositions include an aromatic primary oxidation inhibitor and a secondary or auxiliary sulfur-containing oxidation inhibitor. The sulfur-containing inhibitor is characterized by the formula: EQU R.sub.1 --S (R.sub.2 --O).sub.n --R.sub.3
wherein R.sub.1 is a C.sub.1 -C.sub.20 alkyl group, R.sub.2 is an ethylene or 1,2-propylene alkylene group, R.sub.3 is H, and n is an integer designating the number of alkylene oxide groups. Typically, the average molecular weight of the sulfur-containing secondary inhibitor is between about 250 and 2000.
U.S. Pat. No. 2,750,342 discloses a class of synthetic phosphorous- and sulfur-containing compounds which are useful as lubricating oil additives and which are characterized by the general formula: ##STR2## in which R represents a saturated aliphatic C.sub.2 -C.sub.3 hydrocarbon group, X.sub.1, X.sub.2 and X.sub.3 each represent O or S, and R.sub.1, R.sub.2 and R.sub.3 each represent a C.sub.1 -C.sub.18 alkyl group or a series of saturated aliphatic hydrocarbon groups interlinked by O or S atoms.
U.S. Pat. No. 2,874,192 describes the preparation of mercaptals of long chain hydrocarbon aldehydes and their use as synthetic lubricating oils or anti-oxidants. Compounds of the general formula EQU (RS).sub.2 CHR'
are produced wherein R is a hydrocarbon radical derived from the mercaptan and R' is a hydrocarbon radical derived from the aldehyde. R and R' are both independently long chain (C.sub.8 to C.sub.30) hydrocarbons.
U.S. Pat. No. 2,960,523 discloses phosphoric ester derivatives of hydroxylakyl vinyl sulfides having the general formula: ##STR3## where A is a C.sub.2 -C.sub.6 alkylene group, and R.sub.1 and R.sub.2 each are C.sub.1 -C.sub.4 alkyl groups. The disclosed ester derivatives can be copolymerizable with various acrylic esters to provide copolymers which have utility as flame-proofing agents for textiles and paper products.
U.S. Pat. No. 3,135,804 relates to polyether-thioethers which are prepared by heating alkoxylation products of aliphatic monovalent alcohols with dihydroxyalkyl sulfides at a temperature between 100.degree.-200.degree. C. in the presence of relatively small quantities of acid or acid-forming compounds (generally 0.01-5 wt. %, preferably 0.1-1.5 wt. %) such as p-toluene sulfonic acid, orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, phenylphosphoric acid, diphenylphosphoric acid, ammonium phosphate, sodium phosphate, triethyl phosphate, methyl toluene sulfonate, dimethyl sulfate and maleic anhydride. The polyether-thioethers are suitable for use as lubricants, hydraulic fluids, metal working fluids, heat transfer agents, insulating oils, textile assistants and as solvents or additives to high molecular weight compounds.
U.S. Pat. No. 3,335,189 discloses the preparation of polyether-thioethers of the general formula: EQU R.sub.1 --O--(CHR.sub.2 CHR.sub.3 --O).sub.m --(CHR.sub.4 --CHR.sub.5 --S--CHR.sub.6 --CHR.sub.7 --O).sub.n --(CHR.sub.8 --CHR.sub.9 --O).sub.p --R.sub.10
wherein R.sub.1 and R.sub.10 are linear or branched alkyl radicals of 1 to 22 carbons and R.sub.2 through R.sub.9 represent hydrogen and/or the same or different linear or branched alkyl radicals with 1 to 12 carbon atoms. While m, n and p are whole numbers from 1 to 10. The process disclosed in this patent is carried out at elevated temperatures on the order of 100.degree.-220.degree. C., preferably between 140.degree. and 200.degree. C., in the presence of from about 0.01 to 5 wt. %, preferably 0.1 to 1.5 wt. %, of compounds of trivalent phosphorous, such as phosphorous acid or its salts and esters of phosphorous acid or their salts, or phosphonous acid or its salts, esters, amides or the like. The sole example in this patent discusses the lubricating characteristics of the polyether-thioethers.
U.S. Pat. No. 3,446,738 discloses an ester base lubricating composition comprising an aromatic amine and an organic thiophosphite or thiophosphonate having the formula: ##STR4## wherein X is O or S, at least one X being S; n is 0 or 1, but at least three n's being 1; and R.sub.1, R.sub.2 and R.sub.3 are alkyl or aromatic groups. The organic thiophosphite or thiophosphonate functions as an anti-oxidant.
U.S. Pat. No. 3,426,075 relates to mixed polyphenyl ethers-thioethers useful as synthetic lubricants. These compounds are prepared by reacting sodium or potassium salts of thiophenols with halogen containing diphenyl ethers to produce compounds of the structure: EQU R--S--R.sub.1 --O--R.sub.1 --S--R
wherein R and R.sub.1 are phenyl or substituted phenyl i.e. containing phenoxy or thiophenyl substituents. R and R.sub.1 are limited to phenyl.
U.S. Pat. No. 3,450,771 describes the process for producing organic sulfides from the reaction of mercaptans with alcohols. The process consists of reacting mercaptans of the formula R--SH with alcohols of the formula R'--OH at a temperature of 100.degree. to 300.degree. C. in the presence of an alkali metal hydroxide to produce organic sulfides of the formula R--S--R' wherein R and R' are hydrocarbyl radicals.
U.S. Pat. No. 3,660,497 discloses dodecylether-methyl sulfides of the general formula: EQU C.sub.12 H.sub.25 (OCH.sub.2 CH.sub.2).sub.x --S--R
wherein R is a methyl radical when x=1 or 2, and R is a monovalent acetonyl radical when x=0.
U.S. Pat. No. 4,031,023 relates to the use of hydroxy thioethers as oxidation inhibitors and anti-wear agents for lubricating oils. The hydroxy thioethers are of the formula: ##STR5## wherein R is a hydrocarbon group of from C.sub.1 to C.sub.30 ; R' is independently selected from hydrogen or C.sub.1 to C.sub.20 hydrocarbyl; x and y are independently 2 to 5; z is from zero to 5; q is from zero to 4 and m is from 1 to 5 with the proviso that m+q is from 1 to 6.
The materials are prepared by reacting mercaptans with alkylene oxides or by reacting alpha-olefins with hydroxy containing mercaptans.
U.S. Pat. No. 4,081,387 discloses lubricating compositions comprising a major proportion of lubricating oil and a minor proportion of at least one phosphorous- and sulfur-containing additive of the formula: EQU Y.sup.a --S--Y.sup.b
wherein Y.sup.a is ##STR6## and wherein Z is a saturated or unsaturated hydrocarbyl group; each R.sub.1 and R.sub.2, independently, is a hydrocarbyl, hydrocarbyloxy or hydrocarbylmercapto group having from 1 to 10 carbon atoms; R.sub.3 is hydrogen or a C.sub.1 -C.sub.30 hydrocarbyl group; X is S or O; and Y.sup.b is --R.sub.4 H or --R.sub.4 --S--R.sub.5, wherein R.sub.4 is a C.sub.1 -C.sub.30 divalent hydrocarbyl group and R.sub.5 is H or Y.sup.a. The disclosed lubricating compositions exhibit increased resistance to oxidative degradation and anti-wear properties.
U.S. Pat. No. 4,217,233 describes the use of epithio compounds as lubricant additives useful as extreme pressure or anti-wear agents. The compounds may be characterized by the formula: ##STR7## wherein X is oxygen or sulfur; Y and Z are together a direct bond; Q is hydrogen; and R is branched or unbranched alkyl of from 8 to 22 carbon atoms (claim 1).
U.S. Pat. No. 4,704,217 describes the use of friction modifiers of the formula: ##STR8## in gasoline crankcase oils wherein R is a (C.sub.1 -C.sub.20) hydrocarbyl radical; R' and R" are divalent (C.sub.1 -C.sub.10) alkylene groups; a is an integer of about 1 to about 10 and x+y is a value of about 1 to about 20.
U.S. Pat. No. 4,511,480 discloses phosphite esters of oxyalkylated thiols as corrosion inhibitors for ferrous metals in deep gas wells. The disclosed esters have the formula: ##STR9## where R.sub.1 represents alkyl, cycloalkyl, aryl, aralkyl and heterocyclic; R.sub.2 represents alkyl; x is 1-4, m is 1 or 2; n is 1 when m is 2 and n is 2 when m is 1.
U.S. Pat. No. 4,579,672 discloses lubricating compositions comprising a major portion of lubricating oil and a minor proportion of an oil soluble alkoxypolyethyleneoxy acid phosphite ester providing improved water tolerance properties to the oil. The claimed phosphites are of the structure: ##STR10## wherein, R.sub.1 is alkyl or alkenyl; R.sub.2 is OH, alkoxy or oxyalkenyl or R.sub.1 O(CH.sub.2 CH.sub.2 O).sub.x in which the total number of carbon atoms is 8 to 36 and x is in the range 2 to 4.
U.S. Pat. No. 4,776,969 relates to cyclic phosphates, such as 1,3-dioxa-2-phospha-6-thio-cyclooctane-2-(dodecylthiodiethyleneoxy)-2-oxid e, and their use as an anti-wear, anti-oxidant, and/or friction modifying agent for oleaginous compositions such as fuels and lubricating oils, particularly automatic transmission fluids. The cyclic phosphates can be represented by the formula: ##STR11## where R can represent alkyl, alkenyl, cycloalkyl, aralkyl, alkaryl; n is a number which can vary from 1 to about 3; R.sub.1 is alkylene, n' is a number which can vary from about 1 to about 12; X and X' which may be the same or different can independently represent --O--, --NH-- or --S--; R.sub.2 and R.sub.3 which may be the same or different can independently represent substituted or unsubstituted alkylene; n" can represent the number 0 or 1; and Y can represent --O--, --NH--, --S--, --S--S-- or CH.sub.2 when n" is 1; said R.sub.2 and R.sub.3 being joined together and constituting part: of a cyclic hetero ring structure when n" is 0. The cyclic phosphates may be prepared by reacting an organo phosphorous oxy dichloride and a cyclizing agent such as thiobisethanol. The non-cyclic portion of the cyclic phosphates typically is derived from a hydrocarbyl thioether alcohol which, in turn, can be prepared by reacting a mercaptan and appropriate alkylene oxide or by reacting a terminal olefin with a compound of the formula. HS--(R.sub.1 --O).sub.n' H.
The article "The Condensation of 2-Hydroxyethyl Sulfides with Alcohols and Phenols" by F. Richter, F. B. Augustine, E. Kroft and E. E. Reid, published in Journal of Polymer Science, Vol. XLI, pp 4076-4079, discusses the preparation of ethers by the condensation of alcohols and phenols with 2-hydroxyethyl sulfides using p-toluenesulfonic acids as catalysts.
The article "Thioglycol Polymers I Hydrochloric Acid-Catalyzed Auto Condensation of Thiodiglycol", by Woodward, Journal of Polymer Science, Vol. XLI, pp 219-223 (1959), describes the homopolymerization of thiobisethanol with acid or dehydrating catalyst.
The article "Thioglycol Polymers II Copolymerization of Thiodiglycol and Similar Thioglycols with Aliphatic Hydroxy Compounds", by Andrews et al, Journal of Polymer Science, Vol. XLI, pp 231-239 (1959), describes the acid catalyzed polymerization of thiobisethanol with an alkyl hydroxy or polyhydroxy compound.
U.S. Pat. No. 2,290,880 discloses ethers of alcohol amines which may be used as interface modifying agents in a wide variety of arts. The compounds are said to be useful in lubricating oils and the like, thus enabling the production of effective boring oils, cutting oils, drilling oils, wire drawing oils, extreme pressure lubricants and the like.
U.S. Pat. No. 3,034,907 discloses agents which are effective for hindering or retarding rust formation on iron surfaces and ice formation in the intake system of internal combustion engines. The agents which are disclosed are characterized by a content of (a) a hydrophobic organic carrier, (b) a carboxylic acid amide monocarboxylic acid, and (c) an at least equivalent amount of a hydroxyalkylated nitrogen base which contains at least one lipophilic radical. The hydroxyalkylated nitrogen base corresponds to the general formula: ##STR12## wherein L represents a lipophilic radical; X can represent lower --O-alkylene, --S-alkylene, --O-hydroxyalkylene or --S-hydroxyalkylene, wherein n represents the integer 0 or 1; R.sub.1 represents hydrogen, a lower alkyl or lower hydroxyalkyl or lower aminoalkyl radical; and R.sub.2 is the same as (L-X.sub.n) and R.sub.1. In one embodiment, L represents an aliphatic C.sub.12 -C.sub.18 hydrocarbon radical, n is 0, and at least one of R.sub.1 and R.sub.2 is a low molecular weight hydroxyalkyl or hydroxyalkylaminoethyl radical.
U.S. Pat. No. 3,235,501 discloses foam-inhibited oil compositions which comprise a oleaginous material, a detergent additive, a silicone anti-foamant, and a small amount of a polyalkyl oxylated aliphatic amine which conforms to one of the following formulas (a) or (b) depending on whether the amine from which they are prepared is a mono- or diamine: ##STR13## where R is an aliphatic radical of from about 4 to about 24 carbon atoms, R'O is an alkylene oxide radical selected from the group consisting of the ethylene oxide and propylene oxide radicals, n is an integer from 1 to about 25, and X is selected from hydrogen, R and --(R'O).sub.n H radicals, and ##STR14## where R" is an aliphatic radical having from 2 to about 6 carbon atoms, R'O, n and X are the same as in formula (a), but at least one X is an R radical.
U.S. Pat. No. 3,705,139 discloses alkyl sulfide compounds of the formula: EQU R.sub.1 --S--R.sub.2 --A--(R.sub.3 O).sub.n Z,
where R.sub.1 represents a hydrocarbyl radical having 6 to 22 carbon atoms, R.sub.2 and R.sub.3 each represents a hydrocarbyl radical having 1 to 4 carbon atoms, A can represent nitrogen, n represents an integer in the range of 0-100, and Z can represent hydrogen. The alkyl sulfide compounds are disclosed as being anti-static agents.
U.S. Pat. No. 3,933,659 discloses lubricating oil composition which comprise a major amount of an oil of lubricating viscosity, and an effective amount of each of the following: (1) an alkenyl succinimide, (2) a Group II metal salt of a dihydrocarbyl dithiophosphoric acid, (3) a compound selected from the group consisting of (a) fatty acid esters of dihydric and other polyhydric alcohols, and oil soluble oxyalkylated derivatives thereof, (b) fatty acid amides of low molecular weight amino acids, (c) N-fatty alkyl-N,N diethanol amines, (d) N-fatty alkyl-N,N-di(ethoxyethanol) amines, (e) N-fatty alkyl-N,N-dipoly(ethoxy) ethanol amines, and (f) mixtures thereof, and (4) a basic sulfurized alkaline earth metal alkyl phenate. Such lubricating compositions are useful as functional fluids in systems requiring fluid coupling, hydraulic fluid and/or lubrication of relatively moving parts, particularly as automatic transmission fluids.
U.S. Pat. No. 4,201,684 relates to lubricating oil compositions adapted for use as a crankcase lubricant in internal combustion engines containing a friction reducing amount of a sulfurized fatty acid amide, ester or ester-amide of an oxyalkylated amine.
U.S. Pat. No. 4,231,883 relates to the use of an alkoxylated hydrocarbyl amine in a lubricating oil or fuel to reduce the friction of an internal combustion engine in which the lubricating oil or fuel is used. An example of the alkoxylated hydrocarbyl amine compounds that are disclosed in this patent is N,N-bis(2-hydroxyethyl) oleylamine.
U.S. Pat. No. 4,129,508 relates to lubricant and fuel compositions characterized by improved demulsifying properties. The patent discloses an automatic transmission fluid which includes a number of additives including a dialkyl phosphite, the reaction product of a polyisobutenyl-substituted succinic anhydride, commercial tetraethylene pentamine, and boric acid prepared as set forth in U.S. Pat. No. 3,254,025, and a conventional friction modifier based on polyoxyethylene tallow amine (Ethomeen T/12), the reaction product of polyisobutenyl succinic anhydride and an ethylene polyamine, and Ethomeen C/15. The Ethomeen compounds are available commercially from the Armak Chemical Division of Akzo Chemie.
U.S. Pat. No. 4,170,560 discloses additive compositions for use in crankcase lubricating oils comprising a mixture of an oil soluble anti-oxidant and an oil soluble hydroxyl amine which includes both Ethomeens and Ethoduomeens, which are trade names for compounds available commercially from the Armak Chemical Division of Akzo Chemie.
U.S. Pat. No. 4,382,006 discloses a lubricating composition containing a friction reducing portion of a borated adduct of compounds which include Ethomeens.
U.S. Pat. No. 3,509,052 relates to lubricating compositions containing a lubricating oil, a dispersant which is a derivative of a substituted succinic acid, and a demulsifier. The demulsifier may comprise, for example, an Ethomeen, but the preferred demulsifiers are polyoxyalkylene polyols and derivatives thereof.
U.S. Pat. No. 3,254,025 relates to boron containing acylated amines and lubricating compositions containing them, the amines are produced by reacting a polymer substituted succinic anhydride containing at least about 50 aliphatic carbon atoms with an amine and then reacting this acylated amine product with boron.
U.S. Pat. No. 3,502,677 relates to substituted polyamines which are useful as additives in lubricating compositions, fuels, hydrocarbon oils and power-transmitting fluids. The substituted polyamines are prepared by reacting an alkylene polyamine with a substantially hydrocarbon-substituted succinic acid-producing compound and a phosphorous acid-producing compound.
U.S. Pat. No. 4,615,818 describes oil-soluble sulfurized organic compounds represented by the formula: EQU RS.sub.x R.sub.1
wherein R and R.sub.1 are organic groups. Examples of these organic groups include hydrocarbon groups or substituted hydrocarbon groups containing alkyl, aryl, aralkyl, alkaryl, alkanoate, thiazole, imidazole, phosphorothionate, betaketoalkyl groups, etc. The substantially hydrocarbon groups may contain other substituents such as halogen, amino, hydroxyl, mercapto, alkoxy, aryloxy, thio, nitro, sulfonic acid, carboxylic acid, carboxylic acid ester, etc.
U.S. Pat. No. 4,664,826 relates to metal salt esters of hydrocarbyl substituted succinic acid or anhydride, such as octadecenyl succinic anhydride, and alkanols, such as thiobisethanol, which are capable of exhibiting friction modification, oxidation inhibition, and corrosion inhibition properties in power transmitting fluids such as automatic transmission fluids.
U.S. Pat. No. 4,681,694 discloses a crankcase lubricating oil composition comprising (a) a major portion of a lubricating oil which contains at least one over based calcium alkylphenolate or sulfurized calcium alkylphenolate, a zinc dithiophosphate, and dinonyldiphenylamine, and (b) a rust-inhibiting amount of a dialkoxylated alkylpolyoxyalkyl tertiary amine of the formula: ##STR15## where R is C.sub.1 -C.sub.30 alkyl, n is an integer of about 1 to 6, and x+y is about 2 to 30 where neither x nor y is zero.
U.S. Pat. No. 4,702,850 relates to mineral based power transmitting fluids such as automatic transmission fluid which contain an ester of thiobisalkanol and a C.sub.12 -C.sub.50 hydrocarbon succinic acid or anhydride. The ester functions as a multifunctional additive providing friction modification, corrosion inhibition, anti-wear, oxidation inhibition and extreme pressure properties to the fluids. U.S. Pat. No. 4,664,826 discloses metal salt derivatives of such ester additives.
U.S. Pat. No. 4,764,299 deals with compositions containing sulfur and oxygen which are useful in lubricants and automatic transmission fluids. The compositions are prepared by reacting at least two equivalents of a mercaptan containing at least five carbon atoms and at least two equivalents of a beta-dialkanol. The sulfur and oxygen containing compositions may be illustrated by the formula: EQU RS(AS.sub.x AO).sub.y AS.sub.x ASR.sub.1
wherein x is 1 or greater; y is zero or greater; R and R.sub.1 are hydrocarbyl groups; A is an alkylene group; and at least one of R and R.sub.1 contains at least five carbon atoms.
In an article "Nucleophilic Substitution of Hydroxyl Groups in 2-Alkyl (Aryl)-Thioethanols", published by Fokin et al in the Bull. Acad. Sci. U.S.S.R. Div. Chem. Sci. 1982, Page 1667, there is described the homocondensation of 2-alkylthioethanols. It is also disclosed in the Fokin article that the 2-alkylthioethanol may be reacted with an alcohol under catalysis by strong mineral acids, to give a product containing both sulfur and ether linkages. The mineral acid catalysts disclosed in the Fokin article include HCl, H.sub.3 PO.sub.4, H.sub.2 SO.sub.4, 4-CH.sub.3 C.sub.6 H.sub.4 SO.sub.3 H, HBF.sub.2, HClO.sub.4 and HOSO.sub.2 F. Aromatic sulfur-containing compounds containing beta-hydroxy groups and their reaction properties are also discussed in the Fokin article. The Fokin paper does not discuss any particular utility or special advantage for the compositions described therein.
PCT application WO 88/03554 relates to phosphorous- and/or nitrogen-containing derivative compositions which are useful in fuels, and in lubricating and functional fluid compositions. The derivative compositions comprise a phosphorous- and/or nitrogen-containing derivative composition of sulfur-containing compounds prepared by reacting at least one sulfur composition with either a di- or trihydrocarbyl phosphite, an amine compound containing at least one NH or NH.sub.2 group, or a combination of such phosphite and amine. The sulfur compositions which may be reacted with the phosphite, amine or a combination of phosphite and amine may be characterized by the formula ##STR16## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently H or hydrocarbyl groups; R.sub.1 and/or R.sub.3 may be G.sub.1 or G2; R.sub.1 and R.sub.2 and/or R.sub.3 and R.sub.4 together may be alkylene groups containing about four to about seven carbon atoms; G.sub.1 and G.sub.2 are each independently C(X)R, COOR, C.tbd.N, R.sub.5 --C.dbd.NR.sub.6, or NO.sub.2, and G.sub.1 may be CH.sub.2 OH; X is S or O; and each of R, R.sub.5 and R.sub.6, independently, is H or a hydrocarbyl group. The compositions of this patent also may include at least on carboxylic dispersant composition.